The present invention relates to water soluble, curable compositions of matter. The present invention is more particularly related to water soluble, curable copolymers of vinylpyrrolidone with glycidyl acrylate and acrylamide with glycidyl methacrylate.
In general, there are three polymer systems that are conventionally used as binders for fiberglass, namely phenolic-formaldehyde resins, epoxy resins, and unsaturated polyesters.
While some phenolic-formaldehyde resins may be water soluble, the problem of formaldehyde emission into the environment remains a disadvantage to the use of this type of binder system for fiberglass.
Epoxy resins have traditionally been good binders for fiberglass, as the epoxy resins exhibit satisfactory mechanical properties. Epoxy resins, however, are of high viscosity and are generally insoluble in water and cannot be applied to fiberglass by spraying techniques.
Unsaturated polyesters are also widely used as binders for fiberglass. Generally, unsaturated polyesters are prepared from a diacid and diol. The resulting polyester molecules contain double bonds which can be crosslinked with vinyl monomers, such as styrene. The styrene is traditionally used to create a binder system of low viscosity that is rendered sprayable. The use of styrene, however, remains an environmental problem.
Tashiro et al, U.S. Pat. No. 3,704,229, discloses a water insoluble epoxide curing agent for glycidyl ethers of polyhydric phenols. The curing agent comprises (A) an ester of acrylic or methacrylic acid; (B) a slightly water soluble or water insoluble aliphatic amine; and (C) xylene diamine.
Hirota et al., U.S. Pat. No. 3,954,898, discloses a powder coating of epoxy resin, acrylic copolymer and tertiary amine comprising a copolymer of (A) an alkyl acrylate and (B) glycidyl acrylate or glycidyl methacrylate. The copolymer is further reacted with a cross-linking compound or an epoxy compound in the presence of a tertiary amine.
Anderson, U.S. Pat. No. 4,093,594, discloses a process for preparing cathodically depositable polyepoxide resin compositions comprising: adducting a polyepoxide resin, such as glycidyl polyethers of polyhydric phenols with alkylene polyamines, such as o, m, and p-phenylene diamine and 4,4xe2x80x2-methylene dianiline. The resulting polyepoxide-polyamine adduct is further modified with long chain monoepoxide or monocarboxylic acids.
Bertram et al., U.S. Pat. Nos. 4,250,100 and 4,273,921, disclose water-soluble epoxy resins comprising a glycidyl ether of glycerine and a process for its preparation. The water-soluble epoxy resin of the reference is prepared by the reaction of epoxyalkyl halides, such as epichlorohydrin, and glycerine in the presence of a Lewis Acid. The resulting compound is at least partially dehydrohalogenated with a base or an alkaline-acting material such as potassium hydroxide, sodium hydroxide, sodium and potassium carbonates, hydroxides of magnesium, zinc, lead, iron, aluminum and the like, as well as aluminates, silicates, zincates of alkali metals, to produce the water soluble glycidyl ethers of glycerine.
DeGooyer, U.S. Pat. No. 4,539,347, discloses a novolac based epoxy resin curing agent for use in aqueous systems prepared by reacting a novolac epoxy resin comprising the reaction product of (A) an aldehyde, such as formaldehyde, and (B) a polyphenolic material. The novolac epoxy resin is reacted with a polyalkenamine and end-capped with a monoepoxide or monocarboxylic acid. The epoxy resin curing agent of the reference is salted with acrylic or methacrylic acid to render it water soluble.
DeGooyer, U.S. Pat. No. 4,608,405, discloses an aqueous based epoxy resin curing agent prepared by coreacting a diglycidyl ether of a dihydric phenol, a diglycidyl ether of an aliphatic dihydroxy polyether and a dihydricphenol to form a mixed aliphatic/aromatic polyether diepoxide product. A polyamine is added to the mixed aliphatic/aromatic polyether diepoxide. Finally, the composition is end capped with a monoepoxide or a monocarboxylic acid.
Riew et al., U.S. Pat. No. 5,080,968, discloses composites of vinyl resins and elastomer-coated fibers comprising: (A) a vinyl resin, such as acrylamide and (B) an elastomer-coated fiber material, wherein the coating composition comprises a liquid reactive polymer, such as an acrylate, an aliphatic or aromatic epoxy resin and an amine curing agent, such as the aromatic amines. In a preferred embodiment, graphite fibers are coated with the coating composition, however, the reference discloses that any solid fiber may be coated with the composition.
Yamada et al., U.S. Pat. No. 5,096,954, discloses an aqueous coating composition comprising an acrylic resin and a spiroguanamine resin. The acrylic resin comprises five components, including alkyl-methacrylate.
Gicquel, U.S. Pat. No. 5,178,657, discloses a phenolic binder system for insulating glass fibers comprising: (A) an epoxy resin, based on the reaction product of epichlorohydrin and bisphenol A; (B) an amine hardening (or curing) agent, such as a polyamine; (C) silane; and (D) mineral oil. The binder composition is water dispersable and exhibits low evolution of pollutants.
Chan et al., U.S. Pat. No. 5, 179,172, discloses modified amino compounds, such as imidazole compounds, which are used as curing agents for epoxy resins comprising the reaction product an amino compound and an epichlorohydrin oligomer, a chlorine containing oligomer, or a copolymer of an alkyl acrylate or methacrylate with a chloroethyl vinyl etheralphachlorovinyl acetate.
Gaa et al., U.S. Pat. No. 5,258,227, discloses chemically treated glass fibers with a copolymer of vinylpyrrolidone and acrylate. The composition may further comprise an epoxy copolymer and an amine curing agent.
Ushida et al., U.S. Pat. No. 5,616,363, discloses a binder composition for glass fiber non-woven fabric comprising (A) an epoxy resin, such as a bisphenol A type epoxy resin, (B) a water soluble aliphatic amine curing agent, and (C) an acid to impart solubility to the binder composition.
Zhong et al, U.S. Pat. No. 5,663,258, discloses strongly-swellable, moderately-crosslinked copolymers of vinylpyrrolidone and vinyl acetate (PVP/VA). The PVP/VA copolymer of the Zhong reference is formed by coprecipitation in an organic solvent, such as cyclohexane or heptane, in the presence of a free radical initiator and a crosslinker material, such as N,Nxe2x80x2-divinylimidazolidone, 1-vinyl-3(E)-ethylidene pyrolidone, pentaerythritol triallyl ether, triallyl-1,3,5-triazine-2,4,6(1H,3H,5H)-trione and 2,4,6-triallyloxy-1,3,5-triazine. The resulting PVP/VA copolymer is water insoluble.
Therefore, is remains desirable in the art to provide compositions of matter, binders and coatings that are water-based and which do not involve solvents, that have a low viscosity which results in a sprayable composition, good fiber wettability, heat or ultraviolet curable, good mechanical properties after curing and that are environmentally sound.
It is, therefore, one aspect of the present invention to provide water soluble, curable compositions.
It is another aspect of the present invention is to provide a process for the preparation of water soluble, curable compositions.
It is another aspect of the present invention is to provide binders comprising water soluble, curable compositions.
It is another aspect of the present invention is to provide adhesives comprising water soluble, curable compositions.
It is another aspect of the present invention is to provide coatings comprising water soluble, curable epoxy resins.
The foregoing objects, together with the advantages thereof over the known art relating to water soluble, curable copolymers and binder compositions, which shall become apparent from the specification which follows, are accomplished by the invention as hereinafter described and claimed.
The present invention, therefore, provides a cured composition of matter that is non-swellable in water comprising a water soluble copolymer comprising vinylpyrrolidone and glycidyl acrylate and one of a water soluble aromatic amine or an aliphatic ring amine.
The present invention also provides a cured composition of matter that is non-swellable in water produced by the process comprising the steps of copolymerizing vinylpyrrolidone and glycidyl acrylate; and crosslinking said copolymer of vinylpyrrolidone and glycidyl acrylate with one of a aromatic amine or an aliphatic ring amine.
The present invention also provides a process for preparing a cured composition of matter that is non-swellable in water comprising copolymerizing vinylpyrrolidone with glycidyl acrylate; and crosslinking said copolymer of vinylpyrrolidone and glycidyl acrylate with one of a aromatic amine or an aliphatic ring amine.
The present invention also provides binders, adhesives and coatings comprising a cured composition of matter that is non-swellable in water comprising a cured copolymer of vinylpyrrolidone and glycidyl acrylate.
The present invention also provides a curable, water soluble composition of matter comprising a water soluble copolymer comprising a copolymer of acrylamide and glycidyl methacrylate and one of a water soluble aromatic amine or an aliphatic ring amine.
The present invention also provides a cured composition of matter that is non-swellable in water produced by the process comprising copolymerizing acrylamide with glycidyl methacrylate; and crosslinking said copolymer of acrylamide and glycidyl methacrylate with one of a aromatic amine or an aliphatic ring amine.
The present invention also provides a process for preparing a cured composition of matter that is non-swellable in water comprising copolymerizing acrylamide with glycidyl methacrylate; and crosslinking said copolymer of acrylamide and glycidyl methacrylate with one of a aromatic amine or an aliphatic ring amine.
The present invention also provides binders, adhesives and coatings comprising a cured, water soluble composition of matter comprising a copolymer of acrylamide and glycidyl methacrylate.